Metal to metal bonding for stacked (3d) integrated circuits

ABSTRACT

The present invention provides a stabilized fine textured metal microstructure that constitutes a durable activated surface usable for bonding a 3D stacked chip. A fine-grain layer that resists self anneal enables metal to metal bonding at moderate time and temperature and wider process flexibility.

RELATED APPLICATIONS

This application is a continuation U.S. Ser. No. 14/485,674 filed Sep.13, 2014 which is a continuation of U.S. Ser. No. 13/736,984 filed Jan.9, 2013, now U.S. Pat. No. 8,916,448, the entire contents of which areincorporated herein by reference.

BACKGROUND

Embodiments of present invention relate generally to three dimensional(3D) integrated circuits, and more particularly to enabling themetal-to-metal bonding of integrated circuit substrates at lowtemperature and pressure.

The semiconductor industry continues to drive toward greaterfunctionality and speed of integrated circuits. For the most part, suchimprovements have been achieved by scaling the feature size such thatmore smaller devices can fit in a given area. But such scaling cannotcontinue indefinitely because devices are now approaching atomicdimensions. Furthermore, as the density has increased, so has thecomplexity and length of the interconnect circuitry, causing increasesin both circuit resistance-capacitance (RC) delay and power consumption.Three-dimensional integrated circuits—that is, stacked chips bondedtogether—provides an opportunity to overcome these limitations.

FIG. 1 illustrates a 3D stack 100 in which two semiconductor die arebonded together. Each die may be one of a plurality of dice on a wholeor partial semiconductor wafer, such that 3D stack 100 can represent anycombination such as wafer to wafer, die to wafer, or die to die. A firstdie 110 includes a semiconductor substrate 106 in which at least onesemiconductor device 101 formed and interconnect wiring layer 102, and asecond die 120 includes one or more TSVs (through substrate vias) 121for passing power or signals entirely through the second die 120 to thedevices 101 of the first die. The interconnect wiring 102 is embedded inback end of the line (BEOL) dielectric layers 103, formed on substrate106. The interconnect wiring and TSVs include a conductive core, whichcan be formed of copper. The core is typically separated from thesurrounding materials (e.g., the substrate wafer or dielectric layers)by liner and barrier layers.

The wiring and TSVs are conventionally formed by plating copper onto aseed layer that has been deposited such as by PVD or ALD. The grain sizeof the plated copper depends on the plating conditions and the thicknessof the deposition. This microstructure is known to “self-anneal”, thatis, the thermodynamics favor grain growth, even at room temperature, andeven though this grain growth induces a tensile stress. See Lee andWong, “Correlation of stress and texture evolution during self- andthermal annealing of electroplated Cu films”, J. Appl. Phys 93:43796-3804. Such stresses can cause distortions such as warpage of asilicon wafer. Typical semiconductor processing includes a thermalanneal to accelerate the atomic rearrangement and bring the platedcopper to an equilibrium state.

Controlling the anneal enables further high fidelity processing such asalignment and bonding of two substrates to form the 3D stacked structureof FIG. 1. First die 110 (after completing BEOL processing to form layer103 with interconnect wiring 102) and second die 120 can be bonded bythermocompression bonding between a plated metal (e.g., 105) on thebonding surface 104 of the first die and a plated metal (e.g., 125) onthe bonding surface 124 of the second die. This method may be used indie to die, or die to wafer, as well as for wafer to wafer bonding for3D applications. The facing surfaces of the two die can be formed withmetal regions, for example, a mirror image pattern of copper regions asdepicted in FIG. 2. These metal regions can constitute part of thecircuitry of the final 3D stack, or they can be created strictly asbonding regions. Metal bonding to form the 3 C integrated circuit stackcan be achieved by holding the stack together at temperature of at least350-400 C for at least 30 to 60 minutes.

Unfortunately, such conditions can exceed the thermal budget of delicateintegrated circuitry which cannot be exposed, or at least not forextended time, to high temperature. Farrens reports in “Wafer and DieBonding Technologies for 3D Integration”, MRS Fall 2008 Proceedings E,that lower temperature atomic diffusion of all fcc metals is primarilyalong grain boundaries. Bonding a 3D stack at lower temperatures wouldpermit a wider selection of devices and materials, but has not beenpossible because, as noted above, conventional processing promotes graingrowth such that a plated copper surface has a very low concentration ofgrain boundaries. Even without a thermal anneal, thermodynamics drivesgrain growth and within a very short time converts the surfacemicrostructure of plated copper such that metal to metal bonding attemperature below 350 C is impractical.

A need remains to achieve reliable metal bonding in reasonable time atless stressful conditions.

BRIEF SUMMARY

Embodiments of present invention enables metal to metal bonding at lowerbond temperature and time combination, enabling a lower thermal budget.

According to an embodiment, metal to metal bonding can be enabled byelectroless plating a metal surface to form a bonding layer wherein anaverage grain size of said bonding layer is smaller than an averagegrain size of said metal surface. According to a further embodiment, themetal surface can be oxidized by exposure to H₂O₂, TEAH or TMAH tocreate a roughened surface prior to such electroless plating.

A custom electroless plating solution may include a reducing agentpoison. The custom electroless plating solution may include a depositionpoison. The plating solution may include a contaminant species thatinhibits grain growth in a deposited layer.

According to another embodiment, a 3D stacked structure includes a firstdie bonded to a second die by a metallic bond. The first die includesmetal wiring structure formed within a one or more dielectric layersdisposed on a semiconductor substrate within which at least onesemiconductor device has been formed, and the second die includes asemiconductor substrate having at least one contact pad. The metallicbond is at an interface between said metal structure and said contactpad. A species that inhibits plating other than oxygen is present at theinterface at a concentration substantially higher than the concentrationof such species within either of said metal structure or said contactpad.

In another embodiment, a 3D structure includes a bonding layer upon ametal surface. In yet another embodiment, an interconnect for connectinga first semiconductor die to a second semiconductor die includes thebonding layer upon the metal surface. The average grain size of thebonding layer is smaller than an average grain size of the metalsurface.

BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS

Exemplary embodiments may best be understood by reference to thedetailed description in conjunction with the accompanying figures. TheFigures are provided for illustration and are not drawn to scale.

FIG. 1 depicts a 3D integrated circuit.

FIG. 2 illustrates the bonding surfaces of two substrates comprising a3D integrated circuit structure wherein the surfaces have mirror imagemetal regions within a field of non-conductive material.

FIGS. 3A and 3B illustrate a discontinuous seed layer according tovarious embodiments of the invention.

FIG. 4A, 4B and 4C illustrate pre-treating a bonding surface accordingto embodiments of the invention.

FIG. 5 illustrates an incompletely polished surface amenable totreatment by embodiments of the invention.

DETAILED DESCRIPTION

It will be understood that when an element as a layer, region orsubstrate is referred to as being “on” or “over” another element, it canbe directly on the other element or intervening elements may also bepresent. In contrast, when an element is referred to as being “directlyon” or “directly over” another element, there are no interveningelements present. Similarly, when an element is referred to as being“connected” or “coupled” to another element, it can be directlyconnected or coupled to the other element or intervening elements may bepresent. In contrast, when an element is referred to as being “directlyconnected” or “directly coupled” to another element, there are nointervening elements present. Additionally, to the extent a feature isdescribed to be horizontal or vertical, that orientation is with respectto a generally planar major surface of the substrate which can be in theform of a wafer or disk.

The present invention promotes metal to metal bonding at lowertemperature by forming a layer of fine textured structure on the bondingsurface. Fine metal grains can be deposited and arranged to create alayer of fine textured structure capable of metal to metal surfacebonding at a reduced temperature, that is, at a temperature lower thanthe temperature normally required for metal to metal bonding. A platingstep ordinarily is conducted in such a manner so that clean surfaces aremaintained to enable even metal deposition and growth. Even if a finemetal grain structure could be formed on such a plated surface, themicrostructure is not durable because thermodynamics drives the finegrains to “self-anneal”, that is, to join together to form larger grainsconstituting a lower energy state. The present invention provides astabilized fine textured metal microstructure that constitutes a durableactivated surface even after significant passage of time. Such a finetextured structure can enable metal bonding at lower thermal budget andcan be achieved in various ways.

FIG. 2 illustrates a possible arrangement of the bonding surfaces of the3D stack 100 of FIG. 1. The material of substrate 106 and 126 can be anysemiconductor material including but not limited to group IVsemiconductors such as silicon, silicon germanium, or germanium, a III-Vcompound semiconductor, or a II-VI compound semiconductor. Furthermore,substrates 106 and 126 can be bulk silicon or can comprise layers suchas, silicon/silicon germanium, silicon on insulator (SOI), ETSOI(extremely thin semiconductor on insulator), PDSOI (partially-depletedsemiconductor on insulator) or silicon germanium-on-insulator. Theinsulator layers of these can be referred to as a buried oxide (BOX)layer which can be any insulating oxide such as, e.g., silicon dioxide,or even an epitaxial oxide such as Gadolinium(III)-oxide (Gd₂O₃).

Bonding surface 104 of die 110 can be the top of BEOL layer 103. Assuch, surface 104 can include exposed regions of metal 105 which couldbe the topmost portion of interconnect wiring 102, or they could be padsformed exclusively as bonding structure which does not electricallyconnect to any devices. The remaining portion of surface 104 would bedielectric material such as oxide. Metal regions 105 can be laid out toalign with metal regions 125 on the bonding surface 124 of die 120.

Surface 124 includes metal regions 125 surrounded by a field. It shouldbe understood that FIG. 2 can represent bonding surfaces for die to die,die to wafer, or wafer to wafer bonding. Metal regions of the bondingsurfaces can be as depicted in FIG. 2, with small isolated metal regionsin a dielectric (or other non-metal) field, or could be more of acheckerboard or mixed line pattern. The metal regions 105 and 125 can bemade from a material selected from the group consisting of copper,nickel, copper/nickel, copper/gold and copper/nickel/gold. One or morelayers, e.g. a barrier layer, may separate metal regions fromsurrounding material but are not shown. The field material surroundingregions 125 depends on the design of die 120 and stack 100. For example,if vias 121 were etched into substrate 126 from the side oppositesurface 124, but not all the way through the substrate, and then exposedby thinning the substrate to expose the metal regions 125 of vias 121,then the field could be the material of substrate 126 or it could beanother material such as a passivation material. Another option is thatdie 120 has a BEOL layer (not shown), oriented “face to face” with BEOLlayer 103, in which case the field of surface 124 could be predominantlydielectric material. It should be understood, that first and second die110 and 120 may have similar or different structure or function, andthey can be formed of similar materials such as both having a bulksilicon substrate, but there is no requirement that any analogousstructure be of the same material. The metal of regions 125 can bedifferent from that of 105, provided that they are capable of combiningto permit electron delocalization, i.e., forming a metallic bond. A 3Dstack can also have bonding surfaces that are primarily metal. Forexample U.S. Pat. No. 7,939,369, the specification of which is herebyincorporated by reference, teaches a 3D structure joined by metal tometal bonding, where a metal plane constitutes the last layer of bothdie to be bonded so that each bonding surface is almost completelymetal.

Electroless plating according to embodiments of the present inventioncan be used to activate a bonding surface having isolated bondingregions (such as depicted by FIG. 2), or one comprised primarily bymetal, which is to say it is applicable to joining any two structures byforming a metallic bond. Ordinarily, an electroless solution compositionis carefully controlled to promote deposition of a smooth and continuouslayer, and is designed to maintain clean interfaces as the platingprocess proceeds. The plating solution and the process controls aredesigned to enable and promote continuous films to the thicknessrequired from the plating solution to produce the correct film to meetdesign characteristics. For example a 1 micrometer thick film may berequired for a process and the electroless chemistry is designed toproduce a continuous film that will achieve a 1 micrometer thicknesswithout significant internal imperfection. The standard electrolessplating solution typically includes a source of metal ions; a reducingagent, such as formaldehyde for copper deposition; additives such as tokeep the metal ions in solution or a pH buffer; and a very smallconcentration, such as a few ppm, of a deposition poison, such as lead(Pb) ions, to stop unwanted plating on the tank or transfer equipment.

FIG. 3B illustrates the top or bonding surface 304 of a structure 300,and FIG. 3A illustrates a sideview of structure 300 along a cut at 3A.Structure 300 includes isolated metal regions 305 embedded within anon-metal material 303. Isolated metal regions 305 could be the surface,for example, of BEOL metallization, a contact pad, or a TSV. Metalregions 305 may be annealed to have large average grain size of e.g.,2.0 micron or more. According to the present invention, athermodynamically-stable fine-textured metal layer (having small averagegrain size such as <1.0 or even <0.6 micron or less) can be formed on abonding surface by electroless plating. According to a first embodiment,an activated layer (such as a fine-textured layer) 310 can be formed onmetal regions 305 by exposing bonding surface 304 to a customizedelectroless plating solution that includes, in addition to the usualcomponents, an inhibitor to interfere with metal deposition.

The inhibitor, which may also be referred to as a poison, can beselected from species known to inhibit or stop metal deposition. Theselection and concentration of the inhibitor species depends on theresultant textured surface that is desired. For very fine grain texturedsurfaces, the inhibitor concentration is selected to surface adsorb andpoison small regions 314 on which initial fine grains 310 will not form,at a rate comparable to deposition of fine grains 310 on to regions 315.The chemistry can be tuned so that regions 315 and 314 have roughlyequivalent surface area and have a mean diameter as small as tens ofnanometers. The proper inhibitor concentration appreciates competitivesurface adsorption rates of the inhibitor and metal which is desired tobe plated, and can be tuned for plating onto a freshly plated surface oronto a stabilized or annealed metal surface. The electroless solutionmay include inhibitor at a concentration as low as 100 ppm to as high asseveral hundred thousand ppm dependent on the reactant constant of theinhibitor relative to the reactant constant of the plating system todeposit metal. For example, the solution could include cobalt (Co) ionsin a concentration between 1000 and 10000 ppm, or about 5000 ppm.

Selection of an inhibitor species depends on the particular electrolesschemistry, and can be, for example, one or more of arsenic, cobalt,manganese, chromium, lead, silver, nickel or other metals, metal oxidesof any of the foregoing, and can also be compounds such as, e.g.,acetone, ammonium peroxydisulfate, cerium ammonium nitrate (CAN),2-mercapto-5-benzimidazolesulfonic acid (MBIS), andbis-(3-sulfopropyl)-disulfide (SPS).

According to another embodiment, uniform metal deposition can bedisrupted by interfering with the activity of the plating reducingagent. In that case, an inhibitor to the reducing agent can promoteunequal rates of metal ion reduction (ie, deposition) to produce a finetextured surface. The inhibitor concentration for such embodiment couldbe as low as 100 ppm or several hundred ppm to as high as tens ofthousands ppm dependent on the reactant constant of the inhibitorrelative to the reactant constant of the plating system to depositmetal. The reducing agent inhibitor could be a non-metal or a metalcompound such as a metal ion oxide, or could be, for example, arsenicwithin the range of 100 to 1000 ppm, or at a concentration of about 500ppm.

According to yet another embodiment, activated layer 310 can be formedon a bonding surface 304 by forming a dispersed seed layer. Suchdispersed seed layer could be formed by exposing surface 304 to acustomized seed solution that includes palladium (Pd) or other seedingcatalyst along with a slightly higher concentration of an inhibitor thatpoisons portions of the exposed surface of metal region 305 andpreferentially prohibits uniform seeding. An example of such inhibitorcould be, e.g. lead (Pb) or thallium (TI), at a concentration in therange of 50 to 500 ppm. In particular embodiments the inhibitor could bein the range of 350 to 500 ppm to form seeded regions 315 within amatrix of poisoned regions 314 constituting a discontinuous seed layer.Subsequent electroless deposition can form a fine textured and durableactivated layer 310 on top of the discontinuous seed layer.

The poison species will inhibit seed deposition on regions of theexposed metal, such that the seeded deposition that does occur will be adiscontinuous layer. Optimally each region 315 is very small, such asjust a few seed species, and region 314 has less total surface area thanthe aggregation of all regions 315. In a preferred embodiment, thebonding surface constitutes a finely dispersed composition, such aswhere the mean diameter of regions 315 (ie, the average width of a seedregion) is greater than or at least the same order of magnitude as theaverage edge to edge distance between adjacent seed regions. Electrolessdeposition of layer 310, e.g., copper onto such ‘dispersed seed layer’can maintain a fine grain structure for subsequent bonding because theseed layer constitutes dispersed particles of seed rather than acontinuous film. When subsequently bonded, the fine grained layer 310may anneal with or into the opposite bond surface, but the finelydispersed seed layer will remain as a very thin layer wherein the poisonis at substantially higher concentration than in the bulk of the bondedmaterial. In embodiments, the poison concentration at the interfacecould be more ten times or even several orders of magnitude greater thanits concentration in the bulk of the bonded metal structures. In otherwords, the interface will include a detectible plating poison at aconcentration at least one order of magnitude higher than in theadjacent metal structures. In a preferred embodiment, the poisonconcentration at the interface is at least three orders of magnitudegreater than in the bulk of metal regions 305.

According to yet another embodiment, FIG. 4A depicts subjecting exposedmetal 405 to surface pretreatment such as in H₂O₂, TEAH, TMAH, topromote non-uniform oxide growth 409. For example, according to FIG. 4B,a metal copper surface 406 can be roughened by pre-treatment such as byH₂O₂, followed by a partial surface clean with hydroxyl amine. As shownin FIG. 4C, subsequent plating a film onto such treated surface cancreate a durable activated layer 408 with enhanced roughness and finegrain size.

FIG. 5 illustrates yet another substrate 500 that can be treatedaccording to any embodiment of this invention to form a stable activatedbonding surface. Substrate 500 includes conductive pathways 522 platedto fill patterned openings in a top dielectric layer 503 where a layer528 constitutes a current carrier for electrochemical deposition. CMP toremove excess metal can incompletely remove the barrier layer 528,exposing only small regions of dielectric 503. Surface pretreatment suchas with H₂O₂ can promote non-uniform oxide growth on exposed metal 522as illustrated in FIG. 4. When subsequently subjected to electrolessplating, the differential thickness of this oxide growth, which canpreferentially form along copper grain boundaries, is removed andexposes a rough pristine metal surface. A fine-grained bonding layer canbe deposited onto the rough surface. The roughness helps to stabilize anactivated layer that can be formed with a high density of dislocationsand fine grain structure.

In yet a further embodiment, a contaminant such as tin or silver isincluded in the electroless solution. Such contaminant is selected toco-deposit with the particular metal to be deposited, so that e.g., tindispersed in copper is deposited onto a prepared seed layer. Suchdeposition can be onto a seed layer formed by conventional processing orpreferably onto a finely dispersed seed layer as described above. Thecontaminant, which may constitute from a few ppm up to several percentsuch as 200 ppm to 1.5%, or within the range of 0.01% to 1% of a thinlydeposited layer, can pin the grain boundaries of the deposited metal andthereby enable formation of a stable fine-textured bonding layer. Byinhibiting or delaying grain growth, the deposited bonding layer canmaintain a fine grained microstructure and enable metal to metal bondingat lower temperature, or in less time, or both.

It will be apparent to those skilled in the art having regard to thisdisclosure that other modifications of the exemplary embodiments beyondthose embodiments specifically described here may be made withoutdeparting from the spirit of the invention. Accordingly, suchmodifications are considered within the scope of the invention aslimited solely by the appended claims.

What is claimed is:
 1. A 3D structure comprising: a bonding layer upon ametal surface, wherein an average grain size of the bonding layer issmaller than an average grain size of the metal surface and wherein themetal surface is roughened by exposure to H₂O₂, TEAH, or TMAH.
 2. The 3Dstructure of claim 1, wherein the bonding layer is electrolessly platedupon the metal surface.
 3. The 3D structure of claim 1, wherein thebonding layer is plated upon the metal surface.
 4. The 3D structure ofclaim 1, wherein the metal surface comprises a discontinuous seed layer.5. The 3D structure of claim 1, wherein the metal surface is a surfaceof an interconnect connecting a first semiconductor die to a secondsemiconductor die.
 6. The 3D structure of claim 5, wherein theinterconnect is a through substrate via.
 7. The 3D structure of claim 5,wherein the interconnect is a contact pad.
 8. The 3D structure of claim5, wherein the interconnect is a Back End of Line metallization portion.9. The 3D structure of claim 1, wherein the bonding layer is a finetextured layer.
 10. The 3D structure of claim 1, wherein the averagegrain size of the bonding layer is less than one micron.
 11. The 3Dstructure of claim 1, wherein the average grain size of the bondinglayer is less than 0.6 microns.
 12. The 3D structure of claim 1, whereinthe bonding layer is activated to limit the grains of the active bondinglayer from self annealing with the grains of the metal surface.
 13. Aninterconnect for connecting a first semiconductor die to a secondsemiconductor die, the interconnect comprising: a bonding layer upon ametal surface, wherein an average grain size of the bonding layer issmaller than an average grain size of the metal surface and wherein themetal surface is roughened by exposure to H₂O₂, TEAH, or TMAH.
 14. Theinterconnect of claim 13, wherein the bonding layer is electrolesslyplated upon the metal surface.
 15. The interconnect of claim 13, whereinthe bonding layer is plated upon the metal surface.
 16. The interconnectof claim 13, wherein the metal surface comprises a discontinuous seedlayer.
 17. The interconnect of claim 13, wherein the bonding layer is afine textured layer.
 18. The interconnect of claim 13, wherein theaverage grain size of the bonding layer is less than one micron.
 19. Theinterconnect of claim 13, wherein the average grain size of the bondinglayer is less than 0.6 microns.
 20. The interconnect of claim 13,wherein the bonding layer is activated to limit the grains of the activebonding layer from self annealing with the grains of the metal surface.